Si-containing thin films are used widely in the semiconductor, photovoltaic, LCD-TFT, flat panel-type device, refactory material, or aeronautic industries. Si-containing thin films may be used, for example, as dielectric materials having electrical properties which may be insulating (SiO2, SiN, SiC, SiCN, SiCOH, MSiOx, wherein M is Hf, Zr, Ti, Nb, Ta, or Ge and x is 0-4). Si-containing thin films may also be used as conducting films, such as metal silicides or metal silicon nitrides. Due to the strict requirements imposed by downscaling of electrical device architectures towards the nanoscale (especially below 28 nm node), increasingly fine-tuned molecular precursors are required which meet the requirements of volatility (for vapor processes), lower process temperatures, reactivity with various oxidants and low film contamination, in addition to high deposition rates, conformality and consistency of films produced.
Trisilylamine [N(SiH3)3] has been used for vapor deposition of silicon nitride and silicon oxynitride films (see, e.g., WO2004/030071 to Dussarrat et al.).
Hizawa and Nojimoto (Kogyo Kagaku Zasshi, 1956, 59, 1359-63) describe the synthesis of (Me3SiCH2SiMe2)2NH from the reaction of Me3SiCH2SiMe2Cl and NH3.
Topchiev et als. (Doklady Akademii Nauk SSSR, 1956, 109, 787-90 and Issled. v Obl. Kremniiorgan. Soedin., Sintez i Fiz.-Khim. Svoistva, Akad. Nauk SSSR, Inst. Neftekhim. Sinteza, Sb. Statei, 1962, 130-45) disclose the addition of Br at 5-10° C., and finally at 60-80° C. to R3SiCH2SiR2H yielded R3SiCH2SiR2Br, where R=Me, Et, Pr, or Bu. These in Et2O or MePh were treated with NH3, secondary derivatives being prepared in refluxing MePh, yielding the amine derivatives (R3SiCH2SiR2)2NH, and R3SiCH2SiR2NH2. The secondary derivatives are best prepared from the primary amine derivatives and the mono-Br derivatives by refluxing in MePh followed by passage of NH3 10 hrs.
O'Neill et al. (U.S. Pat. App. Pub. No. 2015/0087139) disclose five classes of organoaminosilane precursors, including H3Si—R3—SiH2—NR1—SiH2—R3—SiH3, wherein R1 is a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cyclic alkyl group, or a C5 to C10 aryl group and R3 is a linear or branched C1 to C10 alkylene group, a linear or branched C3 to C6 alkynylene group, a C3 to C10 cyclic alkylene group, a C3 to C10 hetero-cyclic alkylene group, a C5 to C10 arylene group, or a C5 to C10 hetero arylene group.
Despite the wide range of choices available for the deposition of Si containing films, additional precursors are continuously sought to provide device engineers the ability to tune manufacturing process requirements and achieve films with desirable electrical and physical properties.